KR20000069632A - Composition for dyeing keratin fibres and dyeing method using the same - Google Patents

Abstract

The present invention provides ready-to-use compositions for dyeing keratin fibers, in particular human keratin fibers, such as hair, comprising at least one suitably selected cationic direct dye and at least one nitrobenzene direct dye in a medium suitable for dyeing, But also a dyeing method using this composition.

Description

Dye composition for keratin fibers and dyeing method using the same {COMPOSITION FOR DYEING KERATIN FIBRES AND DYEING METHOD USING THE SAME}

It is known to dye keratin fibers, especially human hair, with dye compositions containing direct dyes, in particular nitrobenzene direct dyes. However, the direct dye has the disadvantage that when included in the dye composition, especially when shampooed, the color development is not sufficiently maintained.

Applicants have found that by combining one or more suitably selected cationic direct dyes with one or more nitrobenzene direct dyes, the present invention is capable of inducing a strong, non-selective coloration that exhibits excellent resistance to various external factors the hair may experience. It was found that dyes can be obtained.

This finding is the basis of the present invention.

The present invention provides compositions for dyeing keratin fibers, in particular human keratin fibers such as hair, as well as compositions comprising at least one cationic direct dye and at least one nitrobenzene dye suitably selected in a medium suitable for dyeing, as well as It relates to the dyeing method used.

The present invention relates, firstly, to ready-to-use compositions for dyeing keratin fibres, in particular human keratin fibres, such as hair, comprising in a medium suitable for dyeing:

At least one cationic direct dye selected from:

a) a compound of formula (I)

[In the above formula:

D is a nitrogen atom or a -CH group,

R ₁ and R ₂ may be the same or different, and are a hydrogen atom; A C _1-4 alkyl radical which may be substituted with a —CN, —OH or —NH ₂ radical; At least one C _1-4 alkyl radical, together with the carbon atoms of the benzene ring; To form any oxygenated or nitrogenous heterocycle which may be substituted with a 4'-aminophenyl radical,

R ₃ and R ' ₃ , which may be the same or different, are hydrogen or a halogen atom selected from chlorine, bromine, iodine and fluorine, or a cyano, C _1-4 alkoxy or acetyloxy radical,

X ⁻ is a preferred anion selected from chloride, methyl sulfate and acetate,

A is a group selected from structures A ₁ to A ₁₉ :

Wherein R ₄ is a C _1-4 alkyl radical which may be substituted with a hydroxy radical, R ₅ is a C _1-4 alkoxy radical, provided that when D is —CH, A is A ₄ or A ₁₃ , When R ₃ is not an alkoxy radical, then R ₁ and R ₂ are not simultaneously hydrogen atoms);

b) a compound of formula II:

[In the above formula:

R ₆ is a hydrogen atom or a C _1-4 alkyl radical;

R ₇ is a hydrogen atom, an alkyl radical which may be substituted with a -CN radical or an amino group, a 4'-aminophenyl radical; Together with R _{6 form} an optional oxygenated and / or nitrogenous heterocycle which may be substituted with a C _1-4 alkyl radical,

R ₈ and R ₉ may be the same or different and are a halogen atom such as a hydrogen atom, bromine, chlorine, iodine or fluorine, a C _1-4 alkyl or C _1-4 alkoxy radical or a -CN radical,

X ⁻ is preferably an anion selected from chloride, methyl sulfate and acetate;

B is a group selected from the structures B1 to B6:

(Wherein R ₁₀ is a C _1-4 alkyl radical, R ₁₁ and R ₁₂ may be the same or different and are a hydrogen atom or a C _1-4 alkyl radical);

c) compounds of the formulas III and III '

[In the above formula:

R ₁₃ is a hydrogen atom, a C _1-4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine or an amino radical,

R ₁₄ is a hydrogen atom, a C _1-4 alkyl radical, or, together with the carbon atom of the benzene ring, forms a heterocycle which is optionally oxygenated and / or substituted with one or more C _1-4 alkyl groups,

R ₁₅ is hydrogen or a halogen atom such as bromine, chlorine, iodine or fluorine,

R ₁₆ and R ₁₇ may be the same or different and are a hydrogen atom or a C _1-4 alkyl radical,

D ₁ and D ₂ may be the same or different and are a nitrogen atom or -CH,

m is 0 or 1,

When R ₁₃ is an unsubstituted amino group, D ₁ and D ₂ are simultaneously a -CH group, m is 0,

X ⁻ is a preferred anion selected from chloride, methyl sulfate and acetate,

E is a group selected from the following structures E1 to E8:

Wherein R 'is a C _1-4 alkyl radical;

When m is 0 and D ₁ is a nitrogen atom, E is a group of the following E9:

(Wherein R 'is a C _1-4 alkyl radical)),

One or more nitrobenzene direct dyes.

The ready-to-use dye compositions of the present invention exhibit a dense, vivid color with low selectivity and excellent resistance in terms of atmospheric factors such as light and bad weather and various treatments (washing, wave-perm) to be subjected to sweat and hair. .

The invention also relates to a method for dyeing keratinous fibers using the ready-to-use composition.

Cationic direct dyes of the formula (I), (II), (III) and (III ′) which can be used in the ready-to-use dye compositions of the invention are known compounds and are described, for example, in WO 95/01772, WO 95/15144 and EP-A-0,714,954. Is disclosed.

Among the cationic direct dyes that can be used in the ready-to-use dye compositions of the invention, mention may be made of the compounds corresponding to the following structures I1 to I52:

Of the compounds of the formulas I1 to I52, the compounds corresponding to the structures I1, I2, I14 and I31 are particularly preferred.

Among the cationic direct dyes of formula II which can be used in the ready-to-use dye compositions of the invention, mention may be made of the compounds corresponding to the following structures II1 to II12:

Among the cationic direct dyes of formula III which can be used in the ready-to-use dye compositions of the invention, mention may be made in particular of the compounds corresponding to the following structures III1 to III18:

Among the specific compounds of the above structures III1 to III18, the compounds corresponding to the structures III4, III5 and III13 are most preferred.

Among the cationic direct dyes of formula III 'which can be used in the ready-to-use dye compositions of the invention, mention may be made in particular of the compounds corresponding to the following structures III'1 to III'3:

The cationic direct dye for use in the present invention is 0.001 to 10% by weight, more preferably 0.05 to 5% by weight relative to the total weight of the ready-to-use dye composition.

The nitrobenzene direct dyes that can be used in the ready-to-use dye compositions of the present invention are preferably selected from compounds of formula IV:

[In the above formula:

-R ₁₈ is an amino radical; C _1-4 alkyl, C _1-4 monohydroxyalkyl, C _2-4 polyhydroxyalkyl, C _1-4 aminoalkyl, mono (C _1-4 ) alkylamino (C _1-4 ) alkyl, di ( C _1-4) alkylamino (C _1-4) alkyl or ureido (C _1-4) alkyl substituted with 1 or 2 substituted amino radical or an aryl radical, or an aryl ring with one or more hydroxy, carboxy, amino, or Aryl radicals which may be substituted with di (C _1-4 ) alkylamino radicals,

-R ₁₉ is a hydrogen atom; Amino radicals; Hydroxy radicals; C _1-4 alkyl radicals; C _1-4 alkoxy radicals; C _1-4 monohydroxyalkyl radicals; C _2-4 polyhydroxyalkyl radicals; C _1-4 monohydroxyalkoxy radicals; C _2-4 polyhydroxyalkoxy radicals; C _1-4 aminoalkoxy radicals; C _1-4 alkyl, C _1-4 monohydroxyalkyl, C _2-4 polyhydroxyalkyl, C _1-4 aminoalkyl, mono (C _1-4 ) alkylamino (C _1-4 ) alkyl, di ( C _1-4) alkylamino (C _1-4) alkyl or ureido (C _1-4) alkyl substituted with 1 or 2 substituted amino radical or an aryl radical, or an aryl ring with one or more hydroxy, carboxy, amino, or An aryl radical substituted with a di (C _1-4 ) alkylamino radical;

R ₂₀ is hydrogen or a halogen atom, a C _1-4 alkyl radical or nitro group.

Among the nitrobenzene dyes of the above formula IV, the following may be mentioned in particular:

2-amino-4-methyl-5-N- (β-hydroxyethyl) aminonitrobenzene,

4-N- (β-ureidoethyl) aminonitrobenzene,

4- (N-ethyl-N-β-hydroxyethyl) amino-1-N- (β-hydroxy-ethyl) aminonitrobenzene,

2-N- (β-hydroxyethyl) amino-5-methylnitrobenzene,

5-chloro-3-N- (ethyl) amino-4-hydroxynitrobenzene,

5-amino-3-chloro-4-hydroxynitrobenzene,

2-N- (γ-hydroxypropyl) amino-5-N, N-bis (β-hydroxyethyl) -aminonitrobenzene,

5-hydroxy-2-N- (y-hydroxypropyl) aminonitrobenzene,

1,3-bis (β-hydroxyethyl) amino-4-chloro-6-nitrobenzene,

2,4-diaminonitrobenzene,

3,4-diaminonitrobenzene,

2,5-diaminonitrobenzene,

3-amino-4-hydroxynitrobenzene,

4-amino-3-hydroxynitrobenzene,

5-amino-2-hydroxynitrobenzene,

2-amino-5-hydroxynitrobenzene,

4-amino-3-hydroxynitrobenzene,

5-amino-2-hydroxynitrobenzene,

2-amino-3-hydroxynitrobenzene,

2-amino-S-N- (β-hydroxyethyl) aminonitrobenzene,

2-amino-5-N, N-bis (β-hydroxyethyl) aminonitrobenzene,

2,5-N, N '-(β-hydroxyethyl) aminonitrobenzene,

2-N- (β-hydroxyethyl) amino-5-N, N-bis (β-hydroxyethyl) -aminonitrobenzene,

2-amino-5-N- (methyl) aminonitrobenzene,

2-N- (methyl) amino-5-N, N-bis (β-hydroxyethyl) aminonitrobenzene,

2-N- (methyl) amino-5- (N-methyl-N-β-hydroxyethyl) aminonitrobenzene,

2,5-N, N '-(β-hydroxyethyl) aminonitrobenzene,

2-N- (β-hydroxyethyl) amino-5-hydroxynitrobenzene,

3-methoxy-4-N- (β-hydroxyethyl) aminonitrobenzene,

2-N- (methyl) amino-4-β-hydroxyethyloxynitrobenzene,

2-amino-3-methylnitrobenzene,

2-N- (β-hydroxyethyl) amino-5-aminonitrobenzene,

2-amino-4-chloro-5-N- (β-hydroxyethyl) aminonitrobenzene,

2-amino-4-methyl-5-N- (β-hydroxyethyl) aminonitrobenzene,

2-amino-4-methyl-5-N- (methyl) aminonitrobenzene,

2-N- (β-hydroxyethyl) amino-5-methoxynitrobenzene,

2-amino-5-β-hydroxyethyloxynitrobenzene,

2-N- (β-hydroxyethyl) aminonitrobenzene,

3-amino-4-N- (β-hydroxyethyl) aminonitrobenzene,

3-β-hydroxyethyloxy-4-N- (β-hydroxyethyl) aminonitrobenzene,

2-N- (methyl) amino-4-β, γ-dihydroxypropyloxynitrobenzene,

2-N- (β-hydroxyethyl) amino-5-β-hydroxyethyloxynitrobenzene,

2-N- (β-hydroxyethyl) amino-5-β, γ-dihydroxypropyloxynitrobenzene,

2-hydroxy-4-N- (β-hydroxyethyl) aminonitrobenzene,

2-N- (methyl) amino-4-methyl-5-aminonitrobenzene,

2-amino-4-isopropyl-5-N- (methyl) aminonitrobenzene,

2-N- (methyl) amino-5- (N-methyl-N-β, γ-dihydroxypropyl) -aminonitrobenzene,

3-N- (β-hydroxyethyl) amino-4-N- (β-hydroxyethyl) aminonitrobenzene,

2-amino-4-methyl-5-N- (β, γ-dihydroxypropyl) aminonitrobenzene,

2-amino-4-methyl-5-hydroxynitrobenzene,

2-N- (β-hydroxyethyl) amino-4-N- (β-hydroxyethyl) aminonitrobenzene,

2-amino-5-N- (β-aminoethyl) aminonitrobenzene,

2-N- (β-aminoethyl) amino-5-methoxynitrobenzene,

2-N- (methyl) amino-5-N- (β-aminoethyl) aminonitrobenzene,

2-N- (β-aminoethyl) amino-4-N, N- (dimethyl) aminonitrobenzene,

3-amino-4-N- (β-aminoethyl) aminonitrobenzene,

2-amino-4-methyl-5-N- (β-aminoethyl) aminonitrobenzene,

2-N- (β-aminoethyl) amino-5-N, N-bis (β-hydroxyethyl) -aminonitrobenzene,

3-β-aminoethyloxy-4-aminonitrobenzene,

2-N- (methyl) amino-5- (N-δ-amino-n-butyl) aminonitrobenzene,

2-N- (y-amino-n-propyl) amino-5-N, N- (dimethyl) aminonitrobenzene,

3-methoxy-4-N- (β-aminoethyl) aminonitrobenzene,

2-N- (β-aminoethyl) amino-5-aminonitrobenzene,

2-amino-4-chloro-5-N- (β-aminoethyl) aminonitrobenzene,

2-N- (β-aminoethyl) amino-4-methoxynitrobenzene,

2-N- (β-aminoethyl) aminonitrobenzene,

2-N- (β-aminoethyl) amino-5-N- (β-aminoethyl) aminonitrobenzene,

2-N- (β-aminoethyl) amino-4-β-hydroxyethyloxynitrobenzene,

3-β-hydroxyethyloxy-4-N- (β-aminoethyl) aminonitrobenzene,

2-amino-5-aminoethyloxynitrobenzene,

3-hydroxy-4-N- (β-aminoethyl) aminonitrobenzene,

2-N- (β-aminoethyl) amino-5-β-hydroxyethyloxynitrobenzene,

2-N- (β-aminoethyl) amino-4-hydroxynitrobenzene,

2-[(2-hydroxy-3-N- (β-hydroxyethyl) amino-6-nitro) benzyloxy] ethylamine, and

2-[(2-hydroxy-3-N- (β-hydroxypropyl) amino-6-nitro) benzyloxy] ethylamine.

Among the nitrobenzene dyes of the above formula IV, the most preferred are as follows:

2-amino-4-methyl-5-N- (β-hydroxyethyl) aminonitrobenzene,

4-N- (β-ureidoethyl) aminonitrobenzene,

4- (N-ethyl-N-β-hydroxyethyl) amino-1-N- (β-hydroxy-ethyl) aminonitrobenzene,

2-N- (β-hydroxyethyl) amino-5-methylnitrobenzene,

5-chloro-3-N- (ethyl) amino-4-hydroxynitrobenzene,

5-amino-3-chloro-4-hydroxynitrobenzene,

2-N- (γ-hydroxypropyl) amino-5-N, N-bis (β-hydroxyethyl) -aminonitrobenzene,

5-hydroxy-2-N- (y-hydroxypropyl) aminonitrobenzene,

1,3-bis (β-hydroxyethyl) amino-4-chloro-6-nitrobenzene,

3,4-diaminonitrobenzene,

2-amino-5-hydroxynitrobenzene,

2-amino-3-hydroxynitrobenzene,

2-amino-5-N- (β-hydroxyethyl) aminonitrobenzene,

2-amino-5-N, N-bis (β-hydroxyethyl) aminonitrobenzene,

2-N- (β-hydroxyethyl) amino-5-N, N-bis (β-hydroxyethyl) -aminonitrobenzene,

2-N- (β-hydroxyethyl) amino-5-hydroxynitrobenzene,

2-N- (β-hydroxyethyl) amino-5-aminonitrobenzene,

2-N- (β-aminoethyl) amino-4-methoxynitrobenzene, and

2-N- (β-aminoethyl) amino-5-β-hydroxyethyloxynitrobenzene.

Nitrobenzene dyes are from 0.0005 to 15% by weight, more preferably from 0.005 to 10% by weight relative to the total weight of the ready-to-use dye composition of the present invention.

Ready-to-use compositions of the present invention may further contain one or more oxidizing bases and / or one or more couplers. Such oxidizing bases can in particular be selected from para-phenylenediamine, para-aminophenol, ortho-phenylenediamine and heterocyclic bases such as pyridine derivatives, pyrimidine derivatives, pyrazole derivatives and pyrazolopyridine derivatives. Couplers are in particular meta-phenylenediamine, meta-aminophenol, meta-diphenol, heterocyclic couplers such as indole derivatives, indolin derivatives, benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives, pyridine, pyri Midine and pyrazole derivatives, and acid addition salts thereof.

The oxidation base, when present in the composition, is present at 0.0005 to 12% by weight, preferably 0.005 to 8% by weight relative to the total weight of the dye composition of the present invention.

The coupler, when present in the composition, is present at 0.0001 to 10% by weight, preferably 0.005 to 5% by weight relative to the total weight of the ready-to-use dye composition.

In general, acid addition salts which can be used in the dye compositions of the invention (oxidation bases and couplers) are selected in particular from hydrochlorides, hydrobromide, sulfates, tartrates, lactates and acetates.

When using one or more oxidizing bases and / or one or more couplers, ready-to-use compositions include, for example, peritises such as hydrogen peroxide, urea peroxide, alkali metal bromates, perborates and persulfates, and peroxidases and 2- It may further contain one or more oxidants selected from enzymes such as electron redox enzymes.

Among the two-electron redox enzymes which can be used as oxidizing agents in the ready-to-use dye compositions of the present invention, mention is made in particular of pyranose oxidase, glucose oxidase, glycerol oxidase, lactate oxidase, pyruvate oxidase and freecase can do.

According to the invention, particular preference is given to using glasscases of animal, microbial or biotechnological origin.

By way of example, mention may be made in particular of glasscases derived from pig liver, Arthrobacter globiformis and Aspergillus flavus.

The 2-electron redox enzyme can be used in pure crystalline form or in a diluted form in a diluent inactive to the 2-electron redox enzyme.

When using a 2-electron redox enzyme, it is used at 0.01 to 20% by weight, preferably 0.1 to 5% by weight relative to the total weight of the ready-to-use dye composition.

When a two-electron redox enzyme is used in the present invention, the ready-to-use composition may also contain one or more donors for that enzyme.

In the present invention, the term "donor" means various substrates associated with the action of the two-electron redox enzyme.

The nature of the donor (or substrate) used will vary depending on the action of the nature of the 2-electron redox enzyme used. For example, D-glucose, L-sorbose and D-xylose are donors of pyranose oxidase, and D-glucose is a donor of glucose oxidase; Glycerol and dihydroxyacetone are donors of glycerol oxidase; Lactic acid and its salts are donors of lactate oxidase; Pyruvic acid and its salts are donors of pyruvate oxidase; Uric acid and its salts are donors of glass case.

When using a donor (or substrate), it is used at 0.01 to 20% by weight, preferably 0.1 to 5% by weight relative to the total weight of the ready-to-use dye composition of the present invention.

Suitable media (or supports) for dyeing the ready-to-use dye compositions of the invention generally consist of water or a mixture of water and one or more organic solvents (to dissolve compounds that are not sufficiently soluble in water). Organic solvents include, for example, C _1-4 alkanols such as ethanol and isopropanol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar products and mixtures thereof.

The pH of the ready-to-use dye composition of the present invention is 5 to 11, preferably 6.5 to 10. Acidifying or basicizing agents generally used for dyeing keratin fibers are adjusted to the desired values.

Among the acidifying agents, there may be mentioned, for example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids (such as acetic acid, tartaric acid, citric acid and lactic acid), and sulfonic acid.

Among the basicizing agents, for example, aqueous ammonia, alkaline carbonates, alkanolamines (eg mono-, di- and triethanolamines), 2-methyl-2-amino-1-propanol and derivatives thereof, sodium hydroxide, Potassium hydroxide and compounds of the formula

[Wherein,

W is a propylene moiety optionally substituted with a hydroxy group or a C _1-4 alkyl radical; R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ may be the same or different and are a hydrogen atom or a C _1-4 alkyl or C _1-4 hydroxyalkyl radical.

The ready-to-use dye compositions of the present invention add various auxiliaries commonly used in hair dye compositions, such as antioxidants, permeants, metal ion sequestrants, fragrances, buffers, dispersants, film formers, preservatives and milk whitening agents. It may contain.

Naturally, one of ordinary skill in the art can select an optimal auxiliary compound to such an extent that the essential properties of the ready-to-use dye compositions of the present invention will not be impaired or substantially impaired by this addition.

The ready-to-use dye compositions of the present invention may be in various forms, such as liquids, creams or gels, which may be pressurized, and may be in other forms especially suitable for dyeing keratinous fibers, such as human hair.

When the ready-to-use dye compositions of the present invention contain at least one oxidizing base and / or at least one coupler, and at least one oxidizing agent, there should be no gaseous oxygen to prevent premature oxidation of the oxidizing dye.

The invention also relates to a method for dyeing keratin fibers, in particular human keratin fibers, such as hair, using the ready-to-use dye compositions as defined above.

According to this method, for a time sufficient to achieve the desired color development, one or more ready-to-use dye compositions as defined above are applied to the fibers, the fibers are rinsed off, optionally rinsed with shampoo, again rinsed and dried.

The time required to develop the keratinous fiber is generally 3 to 30 minutes, more specifically 5 to 40 minutes.

According to an embodiment of the invention, when the dye composition of the invention contains one or more oxidizing bases and / or one or more couplers, on the one hand one or more cationic direct dyes, one or more nitros as defined above in a medium suitable for dyeing Composition A comprising benzene direct dye and at least one oxidizing base and / or at least one coupler, on the other hand, separately storing composition B containing at least one oxidant in a medium suitable for dyeing, and then mixing them when used And then the preceding step consists of applying the mixture to keratinous fibers,

The invention also relates to a multifraction dyeing apparatus or kit comprising a first fraction containing composition A as defined above and a second fraction containing composition B as defined above. Such a device may be provided with a device for applying the desired mixture to the hair, such as the device described in Applicant's patent FR-2,586,913.

The following examples are intended to illustrate the invention, but are not limited thereto.

Dyeing Examples 1 and 2

The following ready-to-use dye compositions are prepared (gram content):

Furtherance One 2 2-amino-5-hydroxynitrobenzene (nitrobenzene direct dye) 0.35 - 2-N- (β-hydroxyethyl) amino-5-amino-nitrobenzene (nitrobenzene direct dye) - 0.25 Orange Cationic Direct Dye Of Structure I4 0.065 - Red Cationic Direct Dye Of Structure I1 - 0.04 Standard dye support (*) (*) (*) Proper amount of deionized water 100 g 100 g

(*): Standard dye support:

20.0 g of ethanol

Oxyethylenated with 9 moles of ethylene oxide

Nonylphenol, Rhodia Chemie

8.0 g available in Igepal NR 9 OR

2-amino-2-methyl-1-propanol titration pH = 7.5

Each of these ready-to-use dye compositions are applied for 30 minutes to a bundle of gray hair containing 90% of white hair. After the hair is rinsed off, it is washed with a standard shampoo and dried.

Hair is dyed in the shades of the table below:

Example Hue obtained One Copper 2 Red mahogany

Claims (29)

Ready-to-use compositions for dyeing keratin fibers, in particular human keratin fibers, such as hair, characterized by comprising in a medium suitable for dyeing: At least one cationic direct dye selected from: a) a compound of formula (I) [In the above formula: D is a nitrogen atom or a -CH group, R ₁ and R ₂ may be the same or different, and are a hydrogen atom; A C _1-4 alkyl radical which may be substituted with a —CN, —OH or —NH ₂ radical; At least one C _1-4 alkyl radical, together with the carbon atoms of the benzene ring; To form any oxygenated or nitrogenous heterocycle which may be substituted with a 4'-aminophenyl radical, R ₃ and R ' ₃ , which may be the same or different, are hydrogen or a halogen atom selected from chlorine, bromine, iodine or fluorine, or a cyano, C _1-4 alkoxy or acetyloxy radical, X ⁻ is a preferred anion selected from chloride, methyl sulfate and acetate, A is a group selected from A ₁ to A ₁₉ : Wherein R ₄ is a C _1-4 alkyl radical which may be substituted with a hydroxy radical, R ₅ is a C _1-4 alkoxy radical, provided that when D is —CH, A is A ₄ or A ₁₃ , When R ₃ is not an alkoxy radical, then R ₁ and R ₂ are not simultaneously hydrogen atoms); b) a compound of formula II: [In the above formula: R ₆ is a hydrogen atom or a C _1-4 alkyl radical; R ₇ is a hydrogen atom, an alkyl radical which may be substituted with a -CN radical or an amino group, a 4'-aminophenyl radical; Together with R _{6 form} an optional oxygenated and / or nitrogenous heterocycle which may be substituted with a C _1-4 alkyl radical, R ₈ and R ₉ may be the same or different and are a halogen atom such as a hydrogen atom, bromine, chlorine, iodine and fluorine, a C _1-4 alkyl or C _1-4 alkoxy radical or —CN radical, X ⁻ is preferably an anion selected from chloride, methyl sulfate and acetate; B is a group selected from the structures B1 to B6: (Wherein R ₁₀ is a C _1-4 alkyl radical, R ₁₁ and R ₁₂ may be the same or different and are a hydrogen atom or a C _1-4 alkyl radical); c) compounds of the formulas III and III ' [In the above formula: R ₁₃ is a hydrogen atom, a C _1-4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine or an amino radical, R ₁₄ is a hydrogen atom, a C _1-4 alkyl radical, or, together with the carbon atom of the benzene ring, forms a heterocycle which is optionally oxygenated and / or substituted with one or more C _1-4 alkyl groups, R ₁₅ is hydrogen or a halogen atom such as bromine, chlorine, iodine or fluorine, R ₁₆ and R ₁₇ may be the same or different and are a hydrogen atom or a C _1-4 alkyl radical, D ₁ and D ₂ may be the same or different and are a nitrogen atom or -CH, m is 0 or 1, When R ₁₃ is an unsubstituted amino group, D ₁ and D ₂ are simultaneously a -CH group, m is 0, X ⁻ is a preferred anion selected from chloride, methyl sulfate and acetate, E is a group selected from the following structures E1 to E8: Wherein R 'is a C _1-4 alkyl radical; When m is 0 and D ₁ is a nitrogen atom, E is a group of the following E9: _Wherein R 'is a C _1-4 alkyl radical) One or more nitrobenzene direct dyes. The composition according to claim 1, wherein the cationic direct dye of formula I is selected from compounds corresponding to structures I1 to I52: The composition of claim 1, wherein the cationic direct dye of formula II is selected from compounds corresponding to structures II1 to II12: The composition of claim 1, wherein the cationic direct dye of formula III is selected from compounds corresponding to structures III1 to III18: The composition of claim 1, wherein the cationic direct dye of formula III 'is selected from compounds corresponding to structures III'1 to III'3: The composition according to claim 1, wherein the cationic direct dye is from 0.001 to 10% by weight relative to the total weight of the ready-to-use dye composition. 7. The composition of claim 6 wherein the cationic direct dye is from 0.05 to 5% by weight relative to the total weight of the ready-to-use dye composition. 8. A composition according to any one of claims 1 to 7, wherein the nitrobenzene direct dye is selected from the compounds of formula IV: [In the above formula: -R ₁₈ is an amino radical; C _1-4 alkyl, C _1-4 monohydroxyalkyl, C _2-4 polyhydroxyalkyl, C _1-4 aminoalkyl, mono (C _1-4 ) alkylamino (C _1-4 ) alkyl, di ( C _1-4) alkylamino (C _1-4) alkyl or ureido (C _1-4) alkyl substituted with 1 or 2 substituted amino radical or an aryl radical, or an aryl ring with one or more hydroxy, carboxy, amino, or Aryl radicals which may be substituted with di (C _1-4 ) alkylamino radicals, -R ₁₉ is a hydrogen atom; Amino radicals; Hydroxy radicals; C _1-4 alkyl radicals; C _1-4 alkoxy radicals; C _1-4 monohydroxyalkyl radicals; C _2-4 polyhydroxyalkyl radicals; C _1-4 monohydroxyalkoxy radicals; C _2-4 polyhydroxyalkoxy radicals; C _1-4 aminoalkoxy radicals; C _1-4 alkyl, C _1-4 monohydroxyalkyl, C _2-4 polyhydroxyalkyl, C _1-4 aminoalkyl, mono (C _1-4 ) alkylamino (C _1-4 ) alkyl, di ( C _1-4) alkylamino (C _1-4) alkyl or ureido (C _1-4) alkyl substituted with 1 or 2 substituted amino radical or an aryl radical, or an aryl ring with one or more hydroxy, carboxy, amino, or An aryl radical substituted with a di (C _1-4 ) alkylamino radical; R ₂₀ is hydrogen or a halogen atom, a C _1-4 alkyl radical or nitro group. The composition of claim 8, wherein the nitrobenzene dye of formula IV is selected from: 2-amino-4-methyl-5-N- (β-hydroxyethyl) aminonitrobenzene, 4-N- (β-ureidoethyl) aminonitrobenzene, 4- (N-ethyl-N-β-hydroxyethyl) amino-1-N- (β-hydroxyethyl) aminonitrobenzene, 2-N- (β-hydroxyethyl) amino-5-methylnitrobenzene, 5-chloro-3-N- (ethyl) amino-4-hydroxynitrobenzene, 5-amino-3-chloro-4-hydroxynitrobenzene, 2-N- (γ-hydroxypropyl) amino-5-N, N-bis (β-hydroxyethyl) -aminonitrobenzene, 5-hydroxy-2-N- (y-hydroxypropyl) aminonitrobenzene, 1,3-bis (β-hydroxyethyl) amino-4-chloro-6-nitrobenzene, 2,4-diaminonitrobenzene, 3,4-diaminonitrobenzene, 2,5-diaminonitrobenzene, 3-amino-4-hydroxynitrobenzene, 4-amino-3-hydroxynitrobenzene, 5-amino-2-hydroxynitrobenzene, 2-amino-5-hydroxynitrobenzene, 4-amino-3-hydroxynitrobenzene, 5-amino-2-hydroxynitrobenzene, 2-amino-3-hydroxynitrobenzene, 2-amino-5-N- (β-hydroxyethyl) aminonitrobenzene, 2-amino-5-N, N-bis (β-hydroxyethyl) aminonitrobenzene, 2,5-N, N '-(β-hydroxyethyl) aminonitrobenzene, 2-N- (β-hydroxyethyl) amino-5-N, N-bis (β-hydroxyethyl) -aminonitrobenzene, 2-amino-5-N- (methyl) aminonitrobenzene, 2-N- (methyl) amino-5-N, N-bis (β-hydroxyethyl) aminonitrobenzene, 2-N- (methyl) amino-5- (N-methyl-N-β-hydroxyethyl) aminonitrobenzene, 2,5-N, N '-(β-hydroxyethyl) aminonitrobenzene, 2-N- (β-hydroxyethyl) amino-5-hydroxynitrobenzene, 3-methoxy-4-N- (β-hydroxyethyl) aminonitrobenzene, 2-N- (methyl) amino-4-β-hydroxyethyloxynitrobenzene, 2-amino-3-methylnitrobenzene, 2-N- (β-hydroxyethyl) amino-5-aminonitrobenzene, 2-amino-4-chloro-5-N- (β-hydroxyethyl) aminonitrobenzene, 2-amino-4-methyl-5-N- (β-hydroxyethyl) aminonitrobenzene, 2-amino-4-methyl-5-N- (methyl) aminonitrobenzene, 2-N- (β-hydroxyethyl) amino-5-methoxynitrobenzene, 2-amino-5-β-hydroxyethyloxynitrobenzene, 2-N- (β-hydroxyethyl) aminonitrobenzene, 3-amino-4-N- (β-hydroxyethyl) aminonitrobenzene, 3-β-hydroxyethyloxy-4-N- (β-hydroxyethyl) aminonitrobenzene, 2-N- (methyl) amino-4-β, γ-dihydroxypropyloxynitrobenzene, 2-N- (β-hydroxyethyl) amino-5-β-hydroxyethyloxynitrobenzene, 2-N- (β-hydroxyethyl) amino-5-β, γ-dihydroxypropyloxynitrobenzene, 2-hydroxy-4-N- (β-hydroxyethyl) aminonitrobenzene, 2-N- (methyl) amino-4-methyl-5-aminonitrobenzene, 2-amino-4-isopropyl-5-N- (methyl) aminonitrobenzene, 2-N- (methyl) amino-5- (N-methyl-N-β, γ-dihydroxypropyl) aminonitrobenzene, 3-N- (β-hydroxyethyl) amino-4-N- (β-hydroxyethyl) aminonitrobenzene, 2-amino-4-methyl-5-N- (β, γ-dihydroxypropyl) aminonitrobenzene, 2-amino-4-methyl-5-hydroxynitrobenzene, 2-N- (β-hydroxyethyl) amino-4-N- (β-hydroxyethyl) aminonitrobenzene, 2-amino-5-N- (β-aminoethyl) aminonitrobenzene, 2-N- (β-aminoethyl) amino-5-methoxynitrobenzene, 2-N- (methyl) amino-5-N- (β-aminoethyl) aminonitrobenzene, 2-N- (β-aminoethyl) amino-4-N, N- (dimethyl) aminonitrobenzene, 3-amino-4-N- (β-aminoethyl) aminonitrobenzene, 2-amino-4-methyl-5-N- (β-aminoethyl) aminonitrobenzene, 2-N- (β-aminoethyl) amino-5-N, N-bis (β-hydroxyethyl) aminonitrobenzene, 3-β-aminoethyloxy-4-aminonitrobenzene, 2-N- (methyl) amino-5- (N-δ-amino-n-butyl) aminonitrobenzene, 2-N- (y-amino-n-propyl) amino-5-N, N- (dimethyl) aminonitrobenzene, 3-methoxy-4-N- (β-aminoethyl) aminonitrobenzene, 2-N- (β-aminoethyl) amino-5-aminonitrobenzene, 2-amino-4-chloro-5-N- (β-aminoethyl) aminonitrobenzene, 2-N- (β-aminoethyl) amino-4-methoxynitrobenzene, 2-N- (β-aminoethyl) aminonitrobenzene, 2-N- (β-aminoethyl) amino-5-N- (β-aminoethyl) aminonitrobenzene, 2-N- (β-aminoethyl) amino-4-β-hydroxyethyloxynitrobenzene, 3-β-hydroxyethyloxy-4-N- (β-aminoethyl) aminonitrobenzene, 2-amino-5-aminoethyloxynitrobenzene, 3-hydroxy-4-N- (β-aminoethyl) aminonitrobenzene, 2-N- (β-aminoethyl) amino-5-β-hydroxyethyloxynitrobenzene, 2-N- (β-aminoethyl) amino-4-hydroxynitrobenzene, 2-[(2-hydroxy-3-N- (β-hydroxyethyl) amino-6-nitro) benzyloxy] ethylamine, and 2-[(2-hydroxy-3-N- (β-hydroxypropyl) amino-6-nitro) benzyloxy] ethylamine. 10. The composition of claim 9, wherein the nitrobenzene dye of formula IV is selected from: 2-amino-4-methyl-5-N- (β-hydroxyethyl) aminonitrobenzene, 4-N- (β-ureidoethyl) aminonitrobenzene, 4- (N-ethyl-N-β-hydroxyethyl) amino-1-N- (β-hydroxyethyl) aminonitrobenzene, 2-N- (β-hydroxyethyl) amino-5-methylnitrobenzene, 5-chloro-3-N- (ethyl) amino-4-hydroxynitrobenzene, 5-amino-3-chloro-4-hydroxynitrobenzene, 2-N- (γ-hydroxypropyl) amino-5-N, N-bis (β-hydroxyethyl) -aminonitrobenzene, 5-hydroxy-2-N- (y-hydroxypropyl) aminonitrobenzene, 1,3-bis (β-hydroxyethyl) amino-4-chloro-6-nitrobenzene, 3,4-diaminonitrobenzene, 2-amino-5-hydroxynitrobenzene, 2-amino-3-hydroxynitrobenzene, 2-amino-5-N- (β-hydroxyethyl) aminonitrobenzene, 2-amino-5-N, N-bis (β-hydroxyethyl) aminonitrobenzene, 2-N- (β-hydroxyethyl) amino-5-N, N-bis (β-hydroxyethyl) -aminonitrobenzene, 2-N- (β-hydroxyethyl) amino-5-hydroxynitrobenzene, 2-N- (β-hydroxyethyl) amino-5-aminonitrobenzene, 2-N- (β-aminoethyl) amino-4-methoxynitrobenzene, and 2-N- (β-aminoethyl) amino-5-β-hydroxyethyloxynitrobenzene. 6. The composition of claim 1, wherein the nitrobenzene dye is 0.0005 to 15% by weight of the ready-to-use dye composition. 7. 12. The composition of claim 11, wherein the nitrobenzene dye is 0.005 to 10% by weight of the ready-to-use dye composition. 13. The meta or phenylenediamine, meta-phenylenediamine according to claim 1, wherein at least one oxidation base and / or meta-phenylenediamine selected from para-phenylenediamine, para-aminophenol, ortho-phenylenediamine and heterocyclic bases. From aminophenols, meta-diphenols, heterocyclic couplers such as indole derivatives, indolin derivatives, benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives, pyridine, pyrimidine and pyrazole derivatives, and acid addition salts thereof A composition comprising at least one coupler selected. 14. The composition of claim 13, wherein the oxidizing base is from 0.0005 to 12% by weight relative to the total weight of the ready-to-use dye composition, and the coupler is from 0.0001 to 10% by weight relative to the total weight of the ready-to-use dye composition. 15. The composition of claim 14, wherein the oxidizing base is from 0.005 to 8% by weight relative to the total weight of the ready to use dye composition and the coupler is from 0.005 to 5% by weight relative to the total weight of the ready to use dye composition. The composition according to any one of claims 13 to 15, wherein the acid addition salt is selected from hydrochloride, hydrobromide, sulfate, tartrate, lactate and acetate. 17. A composition according to any one of claims 13 to 16, which contains at least one oxidizing agent. 18. The composition of claim 17, wherein the oxidizing agent is selected from perchlorates such as hydrogen peroxide, urea peroxide, alkali metal bromate, perborate and persulfate, and enzymes. 19. The composition of claim 18, wherein the enzyme is selected from peroxidases and 2-electron redox enzymes. 20. The composition of claim 19, wherein the two-electron redox enzyme is selected from pyranose oxidase, glucose oxidase, glycerol oxidase, lactate oxidase, pyruvate oxidase and freecase. 21. The composition of claim 19 or 20, wherein the 2-electron redox enzyme is selected from freecases of animal, microbial or biotechnological origin. 22. The composition of any one of claims 19-21, wherein the two-electron redox enzyme is from 0.01 to 20% by weight relative to the total weight of the ready-to-use dye composition. 23. The composition of claim 22 wherein the two-electron redox enzyme is from 0.1 to 5% by weight relative to the total weight of the ready-to-use dye composition. 24. A composition according to any one of claims 21 to 23, containing a donor (or substrate) of a 2-electron redox enzyme selected from uric acid and salts thereof. The composition according to claim 1, wherein the medium suitable for dyeing consists of water or a mixture of water and one or more organic solvents. 26. A composition according to any one of the preceding claims wherein the pH is between 5 and 11. 27. A method comprising applying at least one ready-to-use dye composition as defined in any one of claims 1 to 26 to keratin fibers, in particular human keratin fibers, such as hair, for a time sufficient to achieve the desired color development. How to dye keratin fibers. The method of claim 27, wherein, on the one hand, at least one cationic direct dye, at least one nitrobenzene direct dye and at least one oxidizing base and / or one as defined in any one of claims 1 to 7 in a medium suitable for dyeing. Composition A comprising at least couplers, on the other hand, is separately stored in composition B containing at least one oxidant in a medium suitable for dyeing, which is then mixed when used, and then the mixture is applied to keratin fibers. A dyeing method comprising the previous step made. A multifraction dyeing apparatus or kit comprising a first fraction containing composition A as defined in claim 28 and a second fraction containing composition B as defined in claim 28.